Additives to Enhance Metal and Amine Removal in Refinery Desalting Processes

ABSTRACT

It has been discovered that metals and/or amines can be removed or transferred from a hydrocarbon phase to a water phase in an emulsion breaking process by using a composition that contains water-soluble hydroxyacids. Suitable water-soluble hydroxyacids include, but are not necessarily limited to glycolic acid, gluconic acid, C 2 -C 4  alpha-hydroxy acids, poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic acid, polymeric forms of the above hydroxyacids, poly-glycolic esters, glycolate ethers, and ammonium salt and alkali metal salts of these hydroxyacids, and mixtures thereof. The composition may also include at least one mineral acid to reduce the pH of the desalter wash water. A solvent may be optionally included in the composition. The invention permits transfer of metals and/or amines into the aqueous phase with little or no hydrocarbon phase undercarry into the aqueous phase. The composition is particularly useful in treating crude oil emulsions, and in removing calcium and other metals therefrom.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 12/390,631 filed Feb. 23, 2009, which is adivisional application of U.S. patent application Ser. No. 10/649,921filed Aug. 27, 2003, issued as U.S. Pat. No. 7,497,943 on Mar. 3, 2009,which in turn claims the benefit of U.S. Provisional Application No.60/407,139 filed Aug. 30, 2002.

TECHNICAL FIELD

The present invention relates to methods and compositions for separatingemulsions of hydrocarbons and water, and more particularly relates, inone embodiment, to methods and compositions for transferring metalsand/or amines to an aqueous phase in an emulsion breaking process.

BACKGROUND

In an oil refinery, the desalting of crude oil has been practiced formany years. The crude is usually contaminated from several sources,including, but not necessarily limited to:

-   -   Brine contamination in the crude oil as a result of the brine        associated with the oil in the ground;    -   Minerals, clay, silt, and sand from the formation around the oil        well bore;    -   Metals including calcium, zinc, silicon, nickel, sodium,        potassium, etc.;    -   Nitrogen-containing compounds such as amines used to scrub H₂₅        from refinery gas streams in amine units, or from amines used as        neutralizers in crude unit overhead systems, and also from H₂₅        scavengers used in the oilfield; and    -   Iron sulfides and iron oxides resulting from pipeline and vessel        corrosion during production, transport, and storage.

Desalting is necessary prior to further processing to remove these saltsand other inorganic materials that would otherwise cause fouling anddeposits in downstream heat exchanger equipment and/or form corrosivesalts detrimental to crude oil processing equipment. Further, thesemetals can act as poisons for the catalysts used in downstream refineryunits. Effective crude oil desalting can help minimize the effects ofthese contaminants on the crude unit and downstream operations. Properdesalter operations provide the following benefits to the refiner:

-   -   Reduced crude unit corrosion.    -   Reduced crude preheat system fouling.    -   Reduced potential for distillation column damage.    -   Reduced energy costs.    -   Reduced downstream process and product contamination.

Desalting is the resolution of the natural emulsion of water thataccompanies the crude oil by creating another emulsion in which about 5percent relative wash water is dispersed into the oil using a mix valve.The emulsion mix is directed into a desalter vessel containing aparallel series of electrically charged plates. Under this arrangement,the oil and water emulsion is exposed to the applied electrical field.An induced dipole is formed on each water droplet within the emulsionthat causes electrostatic attraction and coalescence of the waterdroplets into larger and larger droplets. Eventually, the emulsionresolves into two separate phases—the oil phase (top layer) and thewater phase (bottom layer). The streams of desalted crude oil andeffluent water are separately discharged from the desalter.

The entire desalting process is a continuous flow procedure as opposedto a batch process. Normally, chemical additives are injected before themix valve to help resolve the oil/water emulsion in addition to the useof electrostatic coalescence. These additives effectively allow smallwater droplets to more easily coalesce by lowering the oil/waterinterfacial tension.

Crude oil that contains a high percent of particulate solids cancomplicate the desalting process. The particulate solids, by nature,would prefer to transfer to the water phase. However, much of the solidsin a crude oil from a field exists in tight water-in-oil emulsions. Thatis, oil-wetted solids in high concentration in the crude may help formtight oil and water emulsions that are difficult to resolve. These tightemulsions are often referred to as “rag” and may exist as a layerbetween the separated oil and water phases. The rag layer inside thedesalter vessel may grow to such an extent that some of it will beinadvertently discharged with the water phase. This is a problem for thewaste water treatment plant since the rag layer still contains a highpercentage of unresolved emulsified oil.

As mentioned, much of the solids encountered during crude oil desaltingconsists of iron, most commonly as particulate iron such as iron oxide,iron sulfide, etc. Other metals that are desirably removed include, butare not necessarily limited to, calcium, zinc, silicon, nickel, sodium,potassium, and the like, and typically a number of these metals arepresent. Some of the metals may be present in a soluble form. The metalsmay be present in inorganic or organic forms. In addition tocomplicating the desalter operation, iron and other metals are ofparticular concern to further downstream processing. This includes thecoking operation since iron and other metals remaining in the processedhydrocarbon yields a lower grade of coke. Removing the metals from thecrude oil early in the hydrocarbon processing stages is desired toeventually yield high quality coke as well as to limit corrosion andfouling processing problems.

Several treatment approaches have been made to reduce total metal levelsand these all center on the removal of metals at the desalter unit.Normally, the desalter only removes water soluble inorganic salts suchas sodium or potassium chlorides. Some crude oils contain waterinsoluble metal organic acid salts such as calcium naphthenante and ironnaphthenate, which are soluble or dispersed as fine particulate matterin the oil but not in water.

It would thus be desirable to develop a composition and method employingit that would cause most or all of the metals in the crude oil totransfer from the oil phase in a desalter operation, with little or nooil carryunder in the aqueous phase. Nonyl phenol resins have been usedas desalting additives in the past, but these materials have come undersuspicion as possible hormonal mimics and are ineffective by themselvesof removing metals such as calcium or iron.

SUMMARY

Accordingly, it is an object of the present invention to provide acomposition and method of using it that would transfer a large part ofthe metals and/or amines in the crude oil to the aqueous phase in adesalter operation.

It is another object of the present invention to provide a compositionand method for transferring metals and/or amines from a hydrocarbon intoan aqueous phase in an emulsion breaking operation without causing oilundercarry into the aqueous phase.

In carrying out these and other objects of the invention, there isprovided, in one form, a method of transferring metals and/or aminesfrom a hydrocarbon phase to a water phase involving adding to anemulsion of hydrocarbon and water, an effective amount of a compositionto transfer metals and/or amines from a hydrocarbon phase to a waterphase containing at least one water-soluble hydroxyacid. Thewater-soluble hydroxyacid may be glycolic acid, gluconic acid, C₂-C₄alpha-hydroxy acids, poly-hydroxy carboxylic acids, thioglycolic acid,chloroacetic acid, polymeric forms of the above hydroxyacids,poly-glycolic esters, glycolate ethers, and ammonium salt and alkalimetal salts of these hydroxyacids, and mixtures thereof. The emulsion isthen resolved into hydrocarbon phase and an aqueous phase, where atleast a portion of the metals and/or amines have been transferred to theaqueous phase. This is accomplished by converting the water insolublesalt such as calcium naphthenate into a water soluble salt such ascalcium glycolate.

In another non-limiting embodiment of the invention, there is provided acomposition for transferring metals and/or amines from a hydrocarbonphase to a water phase that includes a water-soluble hydroxyacid (asdefined above, including the salts thereof), and a mineral acid.

There is provided in another non-limiting embodiment of the invention acomposition for transferring metals and/or amines from a hydrocarbonphase to a water phase that includes a water-soluble hydroxyacid (asdefined above, including the salts thereof) and at least one additionalcomponent that may be a hydrocarbon solvent, a corrosion inhibitor, ademulsifier, a scale inhibitor, metal chelants, wetting agents andmixtures thereof.

In still another non-limiting embodiment of the invention, there isprovided a treated hydrocarbon emulsion that includes hydrocarbon,water, and a composition for transferring metals and/or amines from ahydrocarbon phase to a water phase comprising a water-solublehydroxyacid (as defined above, including the salts thereof).

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is a graph of various amines and ammonia partitioning acrossdesalters as a function of pH.

DETAILED DESCRIPTION

The inventors have discovered that the addition of glycolic acid(hydroxyacetic acid) and other water-soluble hydroxyacids to a crude oilcan significantly reduce the amount of calcium and other metals and/oramines in the hydrocarbon when it is run through a desalter in arefinery. The inventors have compared the “normal” desalting on areference crude oil containing higher than normal amounts of calcium andfound minimal calcium removal. The addition of glycolic acid in levelsof up to a 5:1 ratio with calcium, results in much lower metals and/oramine content of the desalted oil. The levels of metals other thancalcium such as iron, zinc, silicon, nickel, sodium and potassium arealso reduced. The removal of particulate iron in the form of iron oxide,iron sulfide, etc. is a specific, non-limiting embodiment of theinvention. By “removing” the metals and/or amines from the hydrocarbonor crude is meant any and all partitioning, sequestering, separating,transferring, eliminating, dividing, removing, of one or more metal fromthe hydrocarbon or crude to any extent.

Being an aqueous additive, the glycolic acid is typically added to thewash water in the desalter. This improves distribution of the acid inthe oil although addition to the aqueous phase should not be viewed as arequirement for the composition of the invention to work.

The composition and method of the invention will be valuable to producehigh quality (i.e., high purity) coke from crude that may originallyhave contained high concentrations of metals and/or amines and solids,including iron-based solids. Further, the invention advances thetechnology by removing inorganic material from the crude oil withoutdischarging any oil or emulsion to the waste treatment plant.

In this invention, it will be understood that the metals include, butare not necessarily limited to, those of Groups IA, IIA, VB, VIII, IIBand IVA of the Periodic Table (CAS version). In another non-limitingembodiment, the metals include, but are not necessarily limited tocalcium, iron, zinc, silicon, nickel, sodium, potassium, vanadium, andcombinations thereof. In particular, nickel and vanadium are knownpoisons for catalysts used in fluid catalytic cracking units (FCCUs)downstream.

The amines removed in accordance with the method of this invention mayinclude, but are not necessarily limited to, monoethanolamine (MEA);diethanolamine (DEA); triethanolamine (TEA); N-methylethanolamine;N,N-dimethylethanolamine (DMEA); morpholine; N-methyl morpholine;ethylenediamine (EDA); methoxypropylamine (MOPA); N-ethyl morpholine(EMO); N-methyl ethanolamine, N-methyldiethanolamine and combinationsthereof.

In one embodiment of the invention, the composition of the inventionincludes a water-soluble hydroxy acid. Hydroxy acids are defined hereinas not including or exclusive of acetic acid. Acetic acid has sometimesbeen used to remove metals as well, but it has a high oil solubility andtends to stay with the hydrocarbon coming from the desalter. The acidityof the acetic acid can then cause corrosion problems in the crude unit.The water-soluble hydroxy acids are much more water-soluble and will notpartition as much into the crude oil, thus reducing downstream concerns.They are also less volatile and do not distill into the crude unitoverhead system where they can increase corrosion rates when combinedwith the water usually present at this location.

In one preferred, non-limiting embodiment of the invention, thewater-soluble hydroxyacid is selected from the group consisting ofglycolic acid, C₁-C₄ alpha-hydroxy acids, poly-hydroxy carboxylic acids,thioglycolic acid, chloroacetic acid, polymeric forms of the abovehydroxyacids, glycolate ethers, poly-glycolic esters, and mixturesthereof. While thioglycolic acid and chloroacetic acid are not strictlyspeaking hydroxyacids, they are functional equivalents thereof. For thepurposes of this invention, they are defined as hydroxyacids. The alphasubstituent on the C₁-C₄ alpha-hydroxy acids may be any C₁-C₄ straightor branched alkyl group. In one non-limiting embodiment of theinvention, the alpha substituent may be C₂-C₄ straight or branched alkylgroup and lactic acid is not included. Gluconic acid, CH₂OH(CHOH)₄COOH,is a non-limiting but preferred polymer of glycolic acid. The glycolateethers may have the formula:

where n ranges from 1-10. The glycolate esters may have a formula:

where n is as above. Thioglycolic acid and the ethers of glycolic acidmay have the added benefits of a higher boiling point, and possiblyincreased water solubility. A higher boiling point means the additivewill not distill into the distillate fractions in the crude unit andcause corrosion or product quality concerns. The higher water solubilityalso favors removal of the additive from the crude in the desalter andreduces the amount that may reach the downstream processing units.

In particular, the definition of water-soluble hydroxyacids includesammonium salt and alkali metal salts (e.g. sodium and potassium salts,etc.) of these hydroxyacids alone or in combination with the otherwater-soluble hydroxyacids mentioned. Such salts would be formed in thedesalter wash water as the system's pH was adjusted with pH adjusterssuch as sodium hydroxide, potassium hydroxyide, ammonia, and the like.

In another non-limiting embodiment the water-soluble hydroxyacids do notinclude citric acid, malic acid, tartaric acid, mandelic acid, andlactic acid. In yet another non-limiting embodiment of the invention,the definition of water-soluble hydroxyacids does not include organicacid anhydrides, particularly acetic, propionic, butyric, valeric,stearic, phthalic and benzoic anhydrides.

In yet another non-limiting embodiment of the invention, glycolic acidand gluconic acid may be used to remove calcium and amines, andthioglycolic acid may be used for iron removal, from crude oil oranother hydrocarbon phase.

It is expected that the water-soluble hydroxyacids will be used togetherwith other additives including, but not necessarily limited to,corrosion inhibitors, demulsifiers, pH adjusters, metal chelants, scaleinhibitors, hydrocarbon solvents, and mixtures thereof, in a commercialprocess. Metal chelants are compounds that complex with metals to formchelates. In particular, mineral acids may be used since metal removalis best accomplished at an acidic pH. The use of combinations ofwater-soluble hydroxyacids, particularly glycolic acid or gluconic acid,and mineral acids may give the best economics in a commercialapplication. Suitable mineral acids for use in conjunction with thewater-soluble hydroxyacids of this invention include, but are notnecessarily limited to, sulfuric acid, hydrochloric acid, phosphoricacid, nitric acid, phosphorous acid, and mixtures thereof. As noted, inone embodiment of the invention, the method of this invention ispracticed in a refinery desalting process that involves washing thecrude emulsion with wash water. In one non-limiting embodiment of theinvention, the amount of mineral acid used may be sufficient to lowerthe pH of the wash water to 6 or below. As noted below, in someembodiments of the invention, it may be necessary or preferred to lowerthe pH of the wash water to 5 or below, alternatively to 4 or below. Thewater-soluble hydroxyacids (and salts thereof) are expected to be usefulover a wide pH range, although in some situations it may be necessary ordesirable to adjust the pH to achieve the desired contaminant transferor separation.

It will be appreciated that the necessary, effective or desiredproportions of the hydroxyacid and/or the mineral acid will be difficultto predict in advance, since these proportions or dosages are dependentupon a number of factors, including, but not necessarily limited to, thenature of the hydrocarbon, the concentration of metal species and amineto be removed, the temperature and pressure conditions of method, theparticular hydroxyacid and mineral acid used, etc. In general, the moreof a species, such as calcium, there is to be removed, the more of thereactive acid that must be added. Since many undesirable species areaffected, a successful metal removal process may require more reactiveacid on a stoichiometric basis than would be indicated by theconcentration of only the target species. It may therefore beinsufficient to only just add enough acid to get the pH below 6.Nevertheless, in order to give some sense of the proportions that may beused, in one non-limiting embodiment of the invention, the compositionmay comprise down to about 1 wt. % water-soluble hydroxyacid; and up toabout 20 wt. % mineral acid, preferably from about 1 to about 100 wt. %water-soluble hydroxyacid; and from about 1 to about 20 wt. % mineralacid, and most preferably from about 25 to about 85 wt. % water-solublehydroxyacid; and from about 15 to about 75 wt. % mineral acid. In somenon-limiting embodiments of the invention, the mineral acid is optionaland may be omitted.

The additive blend of this invention is injected into the wash waterbefore the mix valve in neat form or diluted with water, alcohol orsimilar solvent suitable to keep all additive components in solution.The amount of solvent used may range from about 10 to about 95 wt. %,based on the total composition, preferably from about 20 to about 10 wt.%.

The concentration of the additive blend composition of this invention tobe used in the crude oil to be effective is very difficult to predict inadvance since it depends on multiple, interrelated factors including,but not limited to, the composition of the crude, the desaltingconditions (temperature, pressure, etc.), the flow rate of the crude andits residence time in the desalter, among others. Nevertheless, for thepurposes of non-limiting illustration, the proportion of the activewater-soluble hydroxyacid that may be used in the crude (not includingany solvent or mineral acid) may range from about 1 to about 2000 ppm-w,more preferably from about 10 to about 500 ppm-w and will depend on theconcentration of metal species to be removed. The organic hydroxy acidreacts stoichiometrically with the organo metal and/or amine species tobe removed. Thus an equivalent amount of organic hydroxy acid must beadded compared to the concentration of metal species to be removed. Aslight excess of the acid will ensure that the reaction goes tocompletion. In one non-limiting embodiment of the invention, the amountof water-soluble hydroxyacid is stoichiometric with the amount of metalsand/or amines present, or greater than stoichiometric. For economicreasons the refinery may chose to leave some of the metal and/or aminespecies in the crude at an acceptably low level of contamination ofhydrocarbon. In those cases the treatment level of the hydroxy acids canbe correspondingly reduced.

It is most preferred, of course, that in the practice of this inventionthere be no oil carryunder in the aqueous phase, and that at least oilcarryunder is minimized. Further, while it is preferred that all of themetals and/or amines transfer to the aqueous phase, in one non-limitingtheory of the invention, some of the metals and/or amines may betransferred from the oil phase into the rag. This proportion of metalsand/or amines is then removed when the rag is cleaned out.

It is also most preferred, of course, that in the practice of thisinvention all of the metals and/or amines transfer to the aqueous phase.In another non-limiting embodiment of the invention, 25% or less metaland/or amine is present in the hydrocarbon phase after desalting,preferably 20% or less metal and/or amine remains, most preferably only10% or less remains. In some cases the refinery may chose to leavehigher percentages of metal and/or amine contaminants in the crude ifthe detrimental effects are judged to be economically acceptable.

The invention will be illustrated further with reference to thefollowing Examples, which are not intended to limit the invention, butinstead illuminate it further.

The following Electrostatic Desalting Dehydration Apparatus (EDDA) TestMethod was employed to screen possible blend compositions. The EDDA is alaboratory test device to simulate the desalting process.

EDDA Test Method

-   1. Add 800, 600 or 400 ml of crude oil to be tested minus the    percent of wash water (depending on the number of tubes the EDDA    will hold) to a Waring blender.-   2. Add the required percentage of wash water to the blender to bring    the total volume up to 800, 600 or 400 ml.-   3. Mix at 50% speed (on the Variac) for 30 seconds. The speed can be    reduced if the ΔP on the mix valve is low.-   4. Pour the mixture into the EDDA tubes to just below the 100 ml    line.-   5. Place the tubes in the EDDA heating block that is at the desired    test temperature (99° C.).-   6. Add the desired quantity of demulsifier, in ppm, to each tube.    With every test, a blank must be run for comparison purposes.-   7. Place the screw top electrode in the tubes and allow the samples    to heat for approximately 15 minutes.-   8. Tighten the caps and shake each tube 100-200 times and place back    in the heating block to reheat for five minutes.-   9. Place the electrode cover over the tubes and lock into place.    Make sure that there is good contact between the cover and the    electrode caps.-   10. Set the time for five minutes and run at 1500-3000 volts,    depending on the test requirements.-   11. At the end of the five minutes, pull the tubes out and check for    the percent water drop. Also check the quality of the interface and    the quality of the water and record it.-   12. Repeat steps 9, 10, and 11 until the desired total residence    time is achieved.-   13. Determine the best candidates and run a dehydration test on    those samples.    -   a) Fill the desired number of 12.5 ml centrifuge tubes to the        50% mark with xylene.    -   b) Use a glass syringe to pull 5.8 ml of dehydrated crude sample        from the desired level in the tube and mix in with the xylene in        the centrifuge tubes.    -   c) Centrifuge the tubes at 2000 rpm for 4 minutes.    -   d) Check for the quantity of water, emulsion, and solids that        are present in the bottom of the tube and record.

Analysis for Calcium

After completing the EDDA test, use a glass syringe and cannula (long,wide bore needle), to withdraw two 20 ml aliquots of the EDDA desaltedcrude oil. Abstract the oil at a level in the EDDA tube that is at 25 mland 70 ml below the surface of the oil. The two samples (top cut andbottom cut) are each analyzed for calcium concentration by whateverappropriate method (wet ash or microwave digestion, acidification,dilution, AA or ICP analysis). A similar procedure would be used togenerate oil and water samples that could be analyzed by ionchromatography for other contaminants such as amine salts.

The crude oil used was from an African country that has a high calciumcontent.

-   -   Additive A=70% glycolic acid, balance water.    -   Additive B=A blend of glycolic acid, phosphoric acid (pH        adjuster), a pyridine quaternary ammonium compound (corrosion        inhibitor), a dinonyl phenol/ethylene oxide oxyalkylate        (co-solvent), isopropyl alcohol and water.

TABLE I Sample A - 100% Crude Desalted Crude Oil* Top Inter- Water Addi-Raw Crude Phase, face, Phase, Ex. Metal tive Oil, ppm ppm ppm ppm 1Calcium A 370 30 31 1700 2 ″ B 370 76 76 1210 3 Iron A 60 14 15 113 4 ″B 60 26 27 8 5 Zinc A 35 6 4 163 6 ″ B 35 17 16 34 7 Silicon A 37 <2 <26 8 ″ B 37 <2 2 7 9 Nickel A 8 9 9 <2 10 ″ B 8 9 10 <2 11 Sodium A 97 910 416 12 ″ B 97 13 12 404 13 Potassium A 789 31 32 4030 14 ″ B 789 3432 3900 *Top Phase = 20 mL sample taken at 75 mL mark of 100 mL EDDAtest tube. Interface = 20 mL oil sample taken near oil/water interfacepresent in EDDA test tube.

TABLE II Sample B - 20% High Calcium Crude Blend Desalted Crude Oil TopInter- Water Addi- Raw Crude Phase, face, Phase, Ex. Metal tive Oil, ppmppm ppm ppm 15 Calcium A Emulsion Emulsion Emulsion Emulsion 16 ″ B 58 85 362  17 Iron A Emulsion Emulsion Emulsion Emulsion 18 ″ B 10 2 <2    3.6 19 Zinc A Emulsion Emulsion Emulsion Emulsion 20 ″ B  6 5 22  3221 Silicon A Emulsion Emulsion Emulsion Emulsion 22 ″ B <2 11  20   2 23Nickel A Emulsion Emulsion Emulsion Emulsion 24 ″ B  2 3 3 <2 25 SodiumA Emulsion Emulsion Emulsion Emulsion 26 ″ B 17 15  8 113  27 PotassiumA Emulsion Emulsion Emulsion Emulsion 28 ″ B 79 3 4 91

From the data presented above it may be seen that the water-solublehydroxyacid used (glycolic acid) effectively removed or transferred avariety of metals from the oil phase to the water phase. The inventivemethod was particularly effective on the high content metals such ascalcium and potassium.

Tables III-VI provide additional data showing the transfer of variousmetals from a hydrocarbon phase to a water phase using the water-solublehydroxyacids of the invention. The various components are defined asfollows (all proportions are volume percents):

-   Additive C 70% glycolic acid, 30% water-   Additive D 75% Additive C, 20% acrylic acid polymer scale inhibitor    (which alone is designated SI1), 1.8% alkyl pyridine quaternary    ammonium salt corrosion inhibitor, and 3.2% oxyalkylated alkyl    phenol surfactant.-   Additive E 72% phosphorous acid scale control/pH adjuster compound,    14% oxyalkylated polyalkyleneamine, and 14% 511.-   Additive F 10% oxalic acid, 20% thioglycolic acid, 10% glycolic    acid, 1.5% alkyl pyridine quaternary ammonium salt corrosion    inhibitor, and 58.5% water.-   DA through DF designate Demulsifiers A through F, which are all    various oxyalkylated alkylphenol resin demulsifiers. When used    together with an additive of this invention, they may be abbreviated    such as DA/D which indicates Demulsifier A is used together with    Additive D in the ppm ratio given in the next column.-   SI2 Scale Inhibitor 2 that contains diammonium ethylenediamine    tetracetic acid (EDTA).-   SI3 Scale Inhibitor 3 that contains an amine phosphonate scale    inhibitor.-   SRA1 Scale Removal Additive 1, which is a blend of an alkyl pyridine    quaternary ammonium salt corrosion inhibitor (same as in Additive D)    with phosphoric acid, glycolic acid and a demulsifier.

TABLE III EDDA Test Results, Examples 29-40 Test Test Addi- Dose MetalsAnalysis Ex Condition Sample tive (ppm) Na K Mg Ca Fe Cu Zn Al 29 EDDA.Crude A C 1000 Top Oil 2.3 11.5 <1 85 51 <2 40.0 1.5 10% DI (in water)Interface 2.5 8.5 <1 68 40 <2 31.0 1.0 Wash Water Water 443 4400 21.91560 2.7 <0.1 3.7 0.3 30 EDDA. ″ lactic 1000 Top Oil 2.4 6.3 <1 37 39 <230.0 1.2 10% DI acid (in water) Interface 1 6.5 <1 37 38 <2 30.0 1.1Wash Water Water 388 4170 22.1 1610 5.5 <0.1 9.9 0.5 31 EDDA. ″ Blanknone Oil 164 765 4 306 49 <2 30.0 8.0 10% DI Wash Water 32 EDDA. ″ C2000 5 19 <3 24 16 <0.5 2.0 1.2 10% DI (in water) 5 20 <3 24 16 <0.5 2.01.0 Wash Water 425 4670 24 1640 93.8 0.2 162.0 1.5 33 Blank None Oil 87919 5.8 363 68.6 <0.5 32.0 11.4 34 EDDA. ″ SRA1 2000 Top Oil 13 34 76 2617.0 10% DI (in water) Interface 12 32 76 27 16.0 Wash Water Water 4043900 21 1210 8 34.0 35 EDDA. ″ SI2 2000 Top Oil 11 14 192 29 7.0 10% DI(in water) Interface 7 10 191 28 2.0 Wash Water Water 414 4000 20 959 82164.0 36 EDDA. ″ C 2000 Top Oil 9 31 30 14 6.0 10% DI (in water)Interface 10 32 31 15 4.0 Wash Water Water 416 4030 22 1700 113 163.02.0 37 EDDA. ″ SI3 2000 Top Oil 15 60 276 49 38.0 10% DI (in water)Interface 15 60 281 51 39.0 Wash Water Water 440 4190 538 38 EDDA. ″Blank none Oil 97 789 4 370 60 35.0 8.0 10% DI Wash Water 39 EDDA. ″SRA1 2000 Top Oil 15 3 8 2 5.0 10% DI (in water) Interface 8 4 5 22.0Wash Water Water 113 91 6 362 3.6 32.0 40 EDDA. ″ Blank none Oil 17 7958 10 6.0 10% DI Wash Water Test Test Addi- Dose Metals Analysis ExCondition Sample tive (ppm) Sb Ba V Pb Mn Ni Si P 29 EDDA. Crude A C1000 Top Oil 15 2.7 <1 8 10 10.0 1.3 8 10% DI (in water) Interface 152.4 <1 8 8 8.0 <1 8 Wash Water Water <0.1 30.4 <0.1 0.6 18.2 0.2 5.5<0.1 30 EDDA. ″ lactic 1000 Top Oil 14 2.4 <1 7 6 8.0 <1 7 10% DI acid(in water) Interface 20 2.2 <1 10 6 8.0 <1 11 Wash Water Water <0.1 32.3<0.1 0.6 29.4 0.3 5.3 0.1 31 EDDA. ″ Blank none Oil 14 8.5 <1 8 11 7.010 8 10% DI Wash Water 32 EDDA. ″ C 2000 <0.5 0.7 <0.5 11.7 0.6 8.6 30.7<2 10% DI (in water) <0.5 0.7 <0.5 7.9 0.6 9.0 7.1 <2 Wash Water 0.433.8 0.2 3.1 56.4 1.0 5.5 2.2 33 Blank None Oil <0.5 8.4 <0.5 6.8 12.28.4 15.6 2.8 34 EDDA. ″ SRA1 2000 Top Oil 2 93 3 9.0 86 10% DI (inwater) Interface 2 88 3 10.0 2 91 Wash Water Water 8 33 7 1300 35 EDDA.″ SI2 2000 Top Oil 6 80 12.0 45 9 10% DI (in water) Interface 5 84 9.0 26 Wash Water Water 11 4 58 6 36 EDDA. ″ C 2000 Top Oil 94 9.0 5 10% DI(in water) Interface 86 9.0 4 Wash Water Water 31 4 57 6 3 37 EDDA. ″SI3 2000 Top Oil 5 82 13 9.0 14 215 10% DI (in water) Interface 5 95 1310.0 7 223 Wash Water Water 13 7 50 38 EDDA. ″ Blank none Oil 8 48 138.0 37 3 10% DI Wash Water 39 EDDA. ″ SRA1 2000 Top Oil 73 3.0 11 11 10%DI (in water) Interface 59 3.0 20 5 Wash Water Water 12 2 516 40 EDDA. ″Blank none Oil 37 2.0 10% DI Wash Water

TABLE IV EDDA Test Results, Examples 41-54 Test Test Addi- Dose MetalsAnalysis Ex Condition Sample tive (ppm) Na K Mg Ca Fe Cu Zn Al 41 EDDA.Crude A DA 15 Top Oil 5.9 17.1 <3 371 58 <3 36.0 4.0 10% DI WW Water 626<5 17 210 <0.2 <0.2 <0.2 <0.2 42 EDDA. ″ DB 15 Top Oil 5 13 <3 384 60 <336.0 5.0 10% DI WW Water 705 <5 19 236 <0.2 <0.2 <0.2 <0.2 43 EDDA. ″ DC15 Top Oil 11 32 5 443 88 <3 38.0 41.0 10% DI WW Water 579 <5 15 193<0.2 <0.2 <0.2 <0.2 44 EDDA. ″ DD 15 Top Oil 8 27 <3 368 57 <3 36.0 4.010% DI WW Water 698 <5 17 234 <0.2 <0.2 <0.2 <0.2 45 EDDA. ″ DE 15 TopOil 6 23 3 366 55 <3 35.0 4.0 10% DI WW Water 612 <5 16 204 <0.2 <0.2<0.2 <0.2 46 EDDA. ″ Blank None Oil 6 19 <3 361 54 <3 35.0 <3 10% DI WWWater 650 <5 18 216 <0.2 <0.2 <0.2 <0.2 47 EDDA. Crude B DA 15 Top Oil 4<5 <3 40 7 <3 6.0 <3 10% DI WW Water 147 950 7 143 <0.2 <0.2 <0.2 <0.248 EDDA. ″ DB 15 Top Oil 5 <5 <3 41 6 <3 6.0 <3 10% DI WW Water 134 8826 129 <0.2 <0.2 <0.2 <0.2 49 EDDA. ″ DC 15 Top Oil 5 <5 <3 39 7 <3 6.0<3 10% DI WW Water 147 948 7 140 <0.2 <0.2 <0.2 <0.2 50 EDDA. ″ DD 15Top Oil 4 <5 <3 41 6 <3 6.0 <3 10% DI WW Water 148 954 6 140 <0.2 <0.2<0.2 <0.2 51 EDDA. ″ DE 15 6 <5 <3 46 8 <3 6.0 <3 <3 10% DI WW 146 943 7140 <0.2 <0.2 <0.2 <0.2 <0.2 52 EDDA. ″ Blank none Oil 5 <5 <3 48 6 <36.0 <3 10% DI WW Water 130 858 5 122 <0.2 <0.2 <0.2 <0.2 53 EDDA. CrudeC C 50 Top Oil 3 <1 <1 4 2 <1 <1 1.0 10% DI WW Interface 4 <1 <1 3 5 <11.0 1.0 Water 690 42 31 174 124 <1 6.0 2.0 54 EDDA. ″ Blank none Oil 464 3 14 22 <1 2.0 2.0 10% DI WW Test Test Addi- Dose Metals Analysis ExCondition Sample tive (ppm) Sb Ba V Pb Mn Ni Si P 41 EDDA. Crude A DA 15Top Oil <3 5 <3 27 14 10.0 13 4 10% DI WW Water <0.2 7 <0.2 <0.4 <0.2<0.2 10 <0.2 42 EDDA. ″ DB 15 Top Oil <3 5 <3 22 14 10.0 9 3 10% DI WWWater <0.2 8 <0.2 <0.4 <0.2 <0.2 10 <0.2 43 EDDA. ″ DC 15 Top Oil <3 6<3 33 14 11.0 55 3 10% DI WW Water <0.2 7 <0.2 <0.4 <0.2 <0.2 8 <0.2 44EDDA. ″ DD 15 Top Oil <3 6 <3 33 14 10.0 8 4 10% DI WW Water <0.2 9 <0.2<0.4 <0.2 <0.2 9 <0.2 45 EDDA. ″ DE 15 Top Oil <3 5 <3 21 14 10.0 66 <310% DI WW Water <0.2 8 <0.2 <0.4 <0.2 <0.2 8 <0.2 46 EDDA. ″ Blank NoneOil <3 5 <3 20 13 9.0 8 3 10% DI WW Water <0.2 8 <0.2 <0.4 <0.2 <0.2 9<0.2 47 EDDA. Crude B DA 15 Top Oil <3 <3 8 24 <3 <3 6 <3 10% DI WWWater <0.2 2 <0.2 <0.4 <0.2 <0.2 2 <0.2 48 EDDA. ″ DB 15 Top Oil <3 <3 717 <3 <3 6 <3 10% DI WW Water <0.2 2 <0.2 <0.4 <0.2 <0.2 2 <0.2 49 EDDA.″ DC 15 Top Oil <3 <3 7 21 <3 <3 4 <3 10% DI WW Water <0.2 1 <0.2 0.4<0.2 <0.2 3 <0.2 50 EDDA. ″ DD 15 Top Oil <3 <3 7 21 <3 <3 3 <3 10% DIWW Water <0.2 1 <0.2 <0.4 <0.2 <0.2 3 <0.2 51 EDDA. ″ DE 15 6 <3 8 22 <3<3 10 <3 10% DI WW 146 1 <0.2 0.4 <0.2 <0.2 3 <0.2 52 EDDA. ″ Blank noneOil <3 <3 8 23 <3 <3 6 <3 10% DI WW Water <0.2 1 <0.2 0.5 <0.2 <0.2 3<0.2 53 EDDA. Crude C C 50 10% DI WW Top Oil <1 <1 12 <1 <1 6.0 3 3Interface <1 <1 12 <1 <1 6.0 3 3 Water <1 2 <1 <1 <1 <1 2 2 54 EDDA. ″Blank none Oil <1 <1 11 <1 <1 6.0 4 4 10% DI WW

TABLE V EDDA Test Results, Examples 55-67 Test Test Addi- Dose MetalsAnalysis Ex Condition Sample tive (ppm) Na K Mg Ca Fe Cu Zn Al 55 EDDA.Crude DA/D 15/50 Top Oil 6 29 3 225 29 3 15.0 4.0 4% DI WW D/G BlendWater 338 40 383 0.2 <0.1 <0.1 <0.1 56 EDDA. Crude DE/D 15/50 Top Oil 630 4 249 32 4 15.0 3.0 4% DI WW D/G Blend Water 341 34 388 0.2 <0.1 <0.1<0.1 57 EDDA. Crude DB/D 15/50 Top Oil 11 76 4 244 30 5 14.0 2.0 4% DIWW D/G Blend Water 334 35 375 0.1 <0.1 <0.1 <0.1 58 EDDA. Crude DA/D25/50 Top Oil 8 30 2 216 26 7 15.0 3.0 4% DI WW D/G Blend Water 339 39382 0.2 <0.1 <0.1 <0.1 59 EDDA. Crude DE/D 25/50 Top Oil 4% DI WW D/GBlend Water 338 37 380 0.2 <0.1 <0.1 <0.1 60 EDDA. Crude DB/D 25/50 TopOil 13 33 1 206 26 14 15.0 2.0 4% DI WW D/G Blend Water 345 37 386 0.3<0.1 <0.1 <0.1 61 EDDA. Crude Blank None Oil 44 930 11 266 33 2 15.0 4.04% DI WW D/G Blend 62 EDDA. Crude DA/D 40/50 Top Oil 30 20 4 194 29 412.0 4.0 4% DI WW D/G Blend Water 155 18 142 <0.1 <0.1 <0.1 <0.1 63EDDA. Crude DE/D 40/50 Top Oil 6 25 4 205 28 3 13.0 5.0 4% DI WW D/GBlend Water 341 39 292 0.2 <0.1 <0.1 <0.1 64 EDDA. Crude DB/D 40/50 TopOil 8 26 4 224 31 8 17.0 6.0 4% DI WW D/G Blend Water 336 34.2 287 0.2<0.1 <0.1 0.2 65 EDDA. Crude DF/D 40/50 Top Oil 8 43 6 230 36 4 19.011.0 4% DI WW D/G Blend Water 352 33.7 297 0.2 <0.1 <0.1 0.2 66 EDDA.Crude DD/D 40/50 Top Oil 8 67 8 250 34 3 21.0 10.0 4% DI WW D/G BlendWater 344 33 386 0.2 <0.1 0.2 1.0 67 EDDA. Crude DC/D 40/50 Top Oil 7 335 211 34 4 14.0 10.0 4% DI WW D/G Blend Water 352 33.2 300 0.2 <0.1 0.2<0.5 Test Test Addi- Dose Metals Analysis Ex Condition Sample tive (ppm)Sb Ba V Pb Mn Ni Si P 55 EDDA. Crude DA/D 15/50 Top Oil 5 11 8.0 2 11 4%DI WW D/G Blend Water <0.1 17.5 1.1 <0.1 8.1 <0.1 56 EDDA. Crude DE/D15/50 Top Oil 5 12 10.0 3 <1 4% DI WW D/G Blend Water <0.1 17.4 1.1 <0.17.1 <0.1 57 EDDA. Crude DB/D 15/50 Top Oil 5 12 8.0 2 6 4% DI WW D/GBlend Water <0.1 17.3 1.1 <0.1 8 <0.1 58 EDDA. Crude DA/D 25/50 Top Oil5 11 7.0 <1 9 4% DI WW D/G Blend Water <0.1 18.6 1.2 <0.1 9.6 <0.1 59EDDA. Crude DE/D 25/50 Top Oil 4% DI WW D/G Blend Water <0.1 19 1.1 <0.18 <0.1 60 EDDA. Crude DB/D 25/50 Top Oil 5 10 6.0 1 8 4% DI WW D/G BlendWater <0.1 19 1.2 <0.1 8.9 <0.1 61 EDDA. Crude Blank None Oil 7 11 6.0 39 4% DI WW D/G Blend 62 EDDA. Crude DA/D 40/50 Top Oil 3 4 9 3.0 5 14 4%DI WW D/G Blend Water <0.1 6.8 0.6 <0.1 3.5 114 63 EDDA. Crude DE/D40/50 Top Oil 2 5 10 3.0 5 15 4% DI WW D/G Blend Water <0.1 13.6 1.1<0.1 6.9 180 64 EDDA. Crude DB/D 40/50 Top Oil <1 5 10 5.0 2 18 4% DI WWD/G Blend Water <0.1 13.4 1.1 <0.1 7.1 180 65 EDDA. Crude DF/D 40/50 TopOil <1 5 11 6.0 3 18 4% DI WW D/G Blend Water <0.1 13.6 1 <0.1 6.8 18766 EDDA. Crude DD/D 40/50 Top Oil <1 6 12 8.0 4 27 4% DI WW D/G BlendWater <0.1 13.4 1 <0.1 6.7 177 67 EDDA. Crude DC/D 40/50 Top Oil <1 5 104.0 4 14 4% DI WW D/G Blend Water <0.1 13.6 1.1 <0.1 6.7 183

TABLE VI EDDA Test Results, Examples 68-83 Test Test Addi- Dose MetalsAnalysis Ex Condition Sample tive (ppm) Na K Mg Ca Fe Cu Zn Al 68 EDDA.Crude E Blank None Oil 63 1590 12.2 475 23.8 0.5 13.0 0.6 7.5% DI WW 69EDDA. ″ DA/E 30/70 Top Oil 6.1 20.5 7.8 482 25 0.8 14.5 2.1 7.5% DI WWWater 212 2960 25 278 0.7 <0.1 0.1 4.0 70 EDDA. ″ DE/E 30/70 Top Oil 5.617.7 7.4 435 25.2 0.6 14.7 0.5 7.5% DI WW Water 215 2990 27 281 0.7 <0.1<0.1 0.1 71 EDDA. ″ DB/E 30/70 Top Oil 6 17.2 7.7 420 24 0.8 15.1 0.27.5% DI WW Water 218 3020 25.9 283 0.6 <0.1 <0.1 <0.1 72 EDDA. ″ DF/E30/70 Top Oil 6.2 19.6 7.5 485 24.8 0.8 14.7 0.6 7.5% DI WW Water 2293140 29.2 298 0.6 0.2 <0.1 <0.1 73 EDDA. ″ DD/E 30/70 Top Oil 7 18.5 6.6415 24.5 0.4 14.5 <0.4 7.5% DI WW Water 230 3160 28.2 301 0.6 <0.1 <0.1<0.1 74 EDDA. ″ DC/E 30/70 Top Oil 6 24.6 7.6 398 23.4 <0.4 15.0 <0.47.5% DI WW Water 227 3170 28.1 293 0.7 <0.1 <0.1 <0.1 75 EDDA 5.0% CrudeG acetic 1000 Top Oil <0.4 12.6 2.5 22.6 25.2 0.9 10.6 2.1 DI Wash W.acid (in water) Water 116 2430 56.1 3350 72.1 0.5 43.9 <0.1 76 EDDA 5.0%Crude F F 1000 Top Oil 0.8 7 3.9 190 31.8 0.7 15.2 3.0 DI Wash W. (inwater) Water 113 2430 48.3 914 4.6 <0.1 0.7 <0.1 77 EDDA 5.0% Blend EBlank None Oil 11 320 3.3 100 11.3 0.4 4.2 1.1 DI Wash W. 78 EDDA 5.0%+Other acetic 1000 Top Oil 1.4 7.7 1.2 21.5 3.5 <0.4 13.8 9.9 DI Wash W.Crude acid (in water) Water 146 3280 29.7 844 96 0.2 44.9 0.2 79 EDDA5.0% 30/70 F 1000 Top Oil 3 1.2 1 24.7 1.1 <0.4 0.6 1.0 DI Wash W.Refinery (in water) Water 140 3170 29.3 408 118 <0.1 52.4 2.2 80 EDDA5.0% Blend lactic 1000 Top Oil 2.5 25.6 1.3 32.2 2 0.6 1.1 1.0 DI WashW. acid (in water) Water 121 2700 24.1 620 92.5 0.3 37.2 0.7 81 EDDA5.0% ″ glycolic 1000 Top Oil 2.4 22.9 1.2 25.9 2.7 <0.4 0.9 1.5 DI WashW. acid (in water) Water 124 2830 25.2 700 92.2 0.3 38.2 0.6 82 EDDA5.0% ″ SI1 1000 Top Oil 2 7.9 1.9 75 11.1 0.5 5.0 1.1 DI Wash W. (inwater) Water 958 3950 14.3 301 1.4 0.3 0.6 0.3 83 EDDA 5.0% ″ Oxalic1000 Top Oil 6.6 21.9 2.5 80 11.4 0.5 4.7 1.0 DI Wash W. acid (in water)Water 132 2970 20.3 87.4 <0.1 <0.1 <0.1 <0.1 Test Test Addi- Dose MetalsAnalysis Ex Condition Sample tive (ppm) Sb Ba V Pb Mn Ni Si P 68 EDDA.Crude E Blank None Oil <0.4 11 <0.4 <0.4 10.4 10.6 3.9 2.9 7.5% DI WW 69EDDA. ″ DA/E 30/70 Top Oil <0.4 9.2 <0.4 <0.4 11.3 13.2 5.3 26.2 7.5% DIWW Water <0.1 19.3 <0.4 <0.1 1.3 0.5 7.1 291 70 EDDA. ″ DE/E 30/70 TopOil <0.4 9.4 <0.4 <0.4 11.6 13.6 2.4 25.5 7.5% DI WW Water <0.1 19.3<0.4 <0.1 1.3 0.4 7.1 297 71 EDDA. ″ DB/E 30/70 Top Oil <0.4 8.6 <0.4<0.4 11.3 13.8 3.4 27.2 7.5% DI WW Water <0.1 19.8 <0.4 <0.1 1.3 0.7 7.5294 72 EDDA. ″ DF/E 30/70 Top Oil <0.4 9.4 <0.4 <0.4 11.4 14.2 2.6 25.37.5% DI WW Water <0.1 19.8 <0.4 <0.1 1.3 0.9 7.3 313 73 EDDA. ″ DD/E30/70 Top Oil <0.4 8.9 <0.4 <0.4 11.3 13.6 3 26.6 7.5% DI WW Water <0.120.1 <0.4 <0.1 1.3 0.6 7.4 317 74 EDDA. ″ DC/E 30/70 Top Oil <0.4 8.4<0.4 <0.4 10.9 14.8 4 29.2 7.5% DI WW Water <0.1 20.3 <0.1 <0.1 1.4 0.87.8 302 75 EDDA 5.0% Crude G acetic 1000 Top Oil <0.4 0.6 <0.4 <0.4 2.511.6 1.1 4.2 DI Wash W. acid (in water) Water 0.2 84.4 <0.1 0.2 126 0.55.4 0.3 76 EDDA 5.0% Crude F F 1000 Top Oil <0.4 3.9 <0.4 <0.4 12.8 11.72.4 4 DI Wash W. (in water) Water <0.1 44.5 <0.1 <0.1 6.4 <0.1 6.1 0.177 EDDA 5.0% Blend E Blank None Oil <0.4 2.5 <0.4 <0.4 4.1 3.5 0.7 1.5DI Wash W. 78 EDDA 5.0% +Other acetic 1000 Top Oil <0.4 0.9 <0.1 <0.4<0.4 4.1 1.3 2.2 DI Wash W. Crude acid (in water) Water <0.1 14.8 <0.40.3 44.4 0.7 4 0.3 79 EDDA 5.0% 30/70 F 1000 Top Oil <0.4 0.6 <0.1 <0.4<0.4 4.0 <0.4 2.1 DI Wash W. Refinery (in water) Water <0.1 4.2 <0.4<0.1 38.8 0.5 4.9 0.6 80 EDDA 5.0% Blend lactic 1000 Top Oil <0.4 0.9<0.1 <0.4 1.2 3.9 1.8 2 DI Wash W. acid (in water) Water 0.1 10.3 <0.40.7 25.8 36.3 5 0.7 81 EDDA 5.0% ″ glycolic 1000 Top Oil <0.4 0.8 <0.1<0.4 1.1 3.9 2.6 2.2 DI Wash W. acid (in water) Water 0.2 9.8 <0.4 0.927.6 30.7 4.2 0.6 82 EDDA 5.0% ″ SI1 1000 Top Oil <0.4 1.7 <0.1 <0.4 4.23.8 <0.4 1.9 DI Wash W. (in water) Water <0.1 12.6 <0.4 <0.1 3.4 <0.15.4 0.1 83 EDDA 5.0% ″ Oxalic 1000 Top Oil <0.4 1.6 <0.1 <0.4 4.2 3.9<0.4 2.3 DI Wash W. acid (in water) Water <0.1 5.2 <0.4 <0.1 0.7 <0.1 5<0.1

The FIGURE presents a graph showing the partitioning across desalters ofvarious amines and ammonia as a function of pH. The addition ofwater-soluble hydroxyacids of this invention such as glycolic andgluconic acid to the desalter wash water at the use rates specifiedherein will reduce the water's pH to the range of about 3-6.5.

In the foregoing specification, the invention has been described withreference to specific embodiments thereof, and has been demonstrated aseffective in transferring metals, e.g. calcium, potassium, etc., and/oramines from crude oil to the aqueous phase in bench scale desaltingtesting, as non-limiting examples. However, it will be evident thatvarious modifications and changes can be made thereto without departingfrom the broader spirit or scope of the invention as set forth in theappended claims. Accordingly, the specification is to be regarded in anillustrative rather than a restrictive sense. For example, specificwater-soluble hydroxyacids, and combinations thereof with other mineralacids, other than those specifically exemplified or mentioned, or indifferent proportions, falling within the claimed parameters, but notspecifically identified or tried in a particular application to transfermetals and/or amines into the aqueous phase, are within the scope ofthis invention. Similarly, it is expected that the inventivecompositions will find utility as metal transfer compositions for otherfluids besides crude oil emulsions.

1. A method of transferring metals and/or amines from a hydrocarbon phase to a water phase in a process comprising: adding acidic wash water to a crude oil to create an emulsion, where the crude oil comprises metals and/or amines, and where the emulsion comprises a composition comprising at least one water-soluble hydroxyacid selected from the group consisting of glycolic acid, gluconic acid, citric acid, C₂-C₄ alpha-hydroxy acids, malic acid, lactic acid, poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic acid, polymeric forms of the above hydroxyacids, poly-glycolic esters, glycolate ethers, and ammonium salt and alkali metal salts of these hydroxyacids, and mixtures thereof, where the water-soluble hydroxy acid is present in the emulsion in an amount effective to transfer metals and/or amines from a hydrocarbon phase to a water phase; and resolving the emulsion into a hydrocarbon phase and an aqueous phase using electrostatic coalescence, where at least a portion of the metals and/or amines are transferred to the aqueous phase.
 2. The method of claim 1 where in the composition, the composition comprises down to about 1 wt. % water-soluble hydroxyacid.
 3. The method of claim 1 where the water-soluble hydroxyacid is present in the emulsion in an amount ranging from about 1 to about 2000 ppm.
 4. The method of claim 1 where in the composition, the composition further comprises water or alcohol solvent.
 5. The method of claim 1 where the composition additionally comprises at least one additional component selected from the group consisting of a water or alcohol solvent, demulsifiers, corrosion inhibitors, scale inhibitors, metal chelants, wetting agents and mixtures thereof.
 6. The method of claim 1 where the emulsion further comprises at least one demulsifier.
 7. The method of claim 1 where the emulsion further comprises at least one corrosion inhibitor.
 8. The method of claim 1 where the acidic wash water has a pH of 6 or below.
 9. A method of transferring metals and/or amines from a hydrocarbon phase to a water phase in a refinery desalting process comprising: adding acidic wash water to a crude oil to create an emulsion, where the crude oil comprises metals and/or amines, and where the emulsion comprises a composition comprising at least one water-soluble hydroxyacid selected from the group consisting of glycolic acid, gluconic acid, citric acid, C₂-C₄ alpha-hydroxy acids, malic acid, lactic acid, poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic acid, polymeric forms of the above hydroxyacids, poly-glycolic esters, glycolate ethers, and ammonium salt and alkali metal salts of these hydroxyacids, and mixtures thereof, where the water-soluble hydroxy acid is present in the emulsion in an amount effective to transfer metals and/or amines from a hydrocarbon phase to a water phase; and resolving the emulsion into a hydrocarbon phase and an aqueous phase using electrostatic coalescence in the refinery desalting process, where at least a portion of the metals and/or amines are transferred to the aqueous phase.
 10. The method of claim 9 where in the composition, the composition comprises down to about 1 wt. % water-soluble hydroxyacid.
 11. The method of claim 9 where the water-soluble hydroxyacid is present in the emulsion in an amount ranging from about 1 to about 2000 ppm.
 12. The method of claim 9 where in the composition, the composition further comprises water or alcohol solvent.
 13. The method of claim 9 where the composition additionally comprises at least one additional component selected from the group consisting of a water or alcohol solvent, demulsifiers, corrosion inhibitors, scale inhibitors, metal chelants, wetting agents and mixtures thereof.
 14. The method of claim 9 where the emulsion further comprises an additional component selected from the group consisting of at least one demulsifier, at least one corrosion inhibitor, and a combination thereof.
 15. The method of claim 9 where the acidic wash water has a pH of 6 or below.
 16. A method of transferring metals and/or amines from a hydrocarbon phase to a water phase in a refinery desalting process comprising: adding wash water having a pH of 6 or below to crude oil to create an emulsion, where the crude oil comprises metals and/or amines, and where the emulsion comprises a composition comprising: a solvent selected from the group consisting of water, alcohol and mixtures thereof; and at least one water-soluble hydroxyacid selected from the group consisting of glycolic acid, gluconic acid, citric acid, C₂-C₄ alpha-hydroxy acids, malic acid, lactic acid, poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic acid, polymeric forms of the above hydroxyacids, poly-glycolic esters, glycolate ethers, and ammonium salt and alkali metal salts of these hydroxyacids, and mixtures thereof, where the water-soluble hydroxyacid comprises from about 1 to about 85 wt. % of the composition, where the water-soluble hydroxy acid is present in the emulsion in an amount effective to transfer metals and/or amines from a hydrocarbon phase to a water phase; an additional component selected from the group consisting of at least one corrosion inhibitor, at least one demulsifier and a combination thereof; and resolving the emulsion into hydrocarbon phase and an aqueous phase using electrostatic coalescence in the refinery desalting process, where at least a portion of the metals and/or amines are transferred to the aqueous phase.
 17. An acidic composition for transferring metals and/or amines from a hydrocarbon phase to a water phase consisting of: a solvent selected from the group consisting of water, alcohol and mixtures thereof; a water-soluble hydroxyacid selected from the group consisting of glycolic acid, gluconic acid, citric acid, C₂-C₄ alpha-hydroxy acids, malic acid, lactic acid, poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic acid, polymeric forms of the above hydroxyacids, poly-glycolic esters, glycolate ethers, and ammonium salt and alkali metal salts of these hydroxyacids, and mixtures thereof; at least one corrosion inhibitor; and at least one demulsifier.
 18. The composition of claim 17 where the composition further comprises down to about 1 wt. % water-soluble hydroxyacid.
 19. The composition of claim 17 where the water-soluble hydroxyacid comprises from about 1 to about 85 wt % of the composition.
 20. A treated hydrocarbon crude oil emulsion comprising: crude oil; an acidic composition for transferring metals and/or amines from a hydrocarbon phase to a water phase comprising a water-soluble hydroxyacid selected from the group consisting of glycolic acid, gluconic acid, citric acid, C₂-C₄ alpha-hydroxy acids, malic acid, lactic acid, poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic acid, polymeric forms of the above hydroxyacids, poly-glycolic esters, glycolate ethers, and ammonium salt and alkali metal salts of these hydroxyacids, and mixtures thereof; wash water; and at least one additional component selected from the group consisting of a water or alcohol solvent, demulsifiers, scale inhibitors, metal chelants, corrosion inhibitors, wetting agents and mixtures thereof.
 21. The treated crude oil emulsion of claim 20 where the composition further comprises down to about 1 wt. % water-soluble hydroxyacid.
 22. The treated crude oil emulsion of claim 20 where the water-soluble hydroxyacid is present in the emulsion in an amount ranging from about 1 to about 2000 ppm.
 23. The treated crude oil emulsion of claim 20 where the hydrocarbon phase contains more than 10 ppm iron or calcium.
 24. The treated crude oil emulsion of claim 20 where the at least one additional component is at least one demulsifier.
 25. The treated crude oil emulsion of claim 20 where the at least one additional component is at least one corrosion inhibitor.
 26. The treated crude oil emulsion of claim 20 where the wash water is acidic.
 27. The treated crude oil emulsion of claim 26 where the wash water has a pH of 6 or below. 